Photosensitive composition for volume hologram recording, photosensitive medium for volume hologram recording and volume hologram

ABSTRACT

The volume hologram recording photosensitive composition provided by the present invention contains at least a fluorine-contained photoreactive compound represented by the following formula (1): R 1 —R 3 —(CF 2 )n-R 4 —R 2  wherein R 1  and R 2  are photoreactive groups which can be bonded to each other by photoreaction, and each of R 3  and R 4  is independently a single bond or a bivalent hydrocarbon group having 1 to 5 carbon atoms, and n is an integer of 1 or more. This volume hologram recording photosensitive composition is used to form a recording section of a recording medium, and then the section is exposed to light, whereby a bright volume hologram can be obtained.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation application of U.S. Ser. No.10/615,041 filed on Jul. 8, 2003, which has been granted as U.S. Pat.No. 7,824,822.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a new photosensitive compositioncapable of recording a volume hologram, a volume hologram recordingmedium using the same, and a volume hologram produced using thephotosensitive composition.

2. Description of the Related Art

A volume hologram is produced by allowing object lights (object waves)and reference lights (reference waves) each having high coherency(interfering ability) and an equal wavelength to interfere with eachother, radiating the resultant lights into a layer made of volumehologram recording material, and recording three-dimensional informationabout the object, as interference fringes, inside the recording materiallayer. The interference fringes can be recorded, for example, as avariation in the refractive index (a change in the refractive index)corresponding to bright or dark regions of interference light, insidethe recording material layer. Volume holograms are widely used infields, for example, for design purpose, security purpose, opticalelement purpose and others since the volume holograms make it possibleto represent an object three-dimensionally, have high diffractionefficiency and wave selectivity, and need high-level producingtechnique.

As photosensitive compositions for producing volume holograms, anOmniDex series available from Du Pont is only one present in the marketunder mass-production. This material is a dry-developable typephotopolymer material which uses a radical polymerizable monomer, abinder resin, a photo-radical polymerization initiator and a sensitizingdye as its major components and make use of a difference in refractiveindex between the radical polymerizable monomer and the binder resin.That is, when the photosensitive composition formed into a film issubjected to hologram-exposure (exposure for recording holograms),radical polymerization is initiated in regions where the light isintense and a gradient of the concentration of the radical polymerizablemonomer is generated accordingly. Thus, the radical polymerizablemonomer molecules diffuse and move from regions where the light is weakto the regions where the light is intense. As a result, the radicalpolymerizable monomers can be made dense or thin dependently on theintensity or weakness of the interfere light, so that a refractive indexdifference is generated. This material system has the best performanceamong volume holograms photopolymers which have been reported up to thepresent time. However, it has been pointed out that the system hasproblems about heat resistance and transparency. As described above,usually, a hologram-exposure is performed by allowing object waves andreference waves to interfere with each other and be radiated intoregions where images are to be recorded. However, it is also possible toperform a hologram-exposure by using of light having no coherency.

A material system using radical polymerization and cationicpolymerization together is reported. For example, Japanese Patent No.2873126 discloses a system using a monomer having a diarylfluoreneskeleton as a high refractive index radical polymerizable monomer and acationic polymerizable monomer which has a lower refractive index thanthe radical polymerizable monomer. In this system, the high refractiveindex components are polymerized by radical polymerization at the timeof hologram-exposure, and subsequently the images are fixed by cationicpolymerization at time of fixation-exposure.

A material system using cationic polymerization is also disclosed in,for example, U.S. Pat. No. 5,759,721. This material system has anadvantage of being free from such oxygen inhibition as seen in a radicalpolymerization system. However, this system has problems that it has lowphotosensitivity (photospeed) to cationic polymerization and it isdifficult to provide this system with sensitivity in a long-wavelengthrange.

Moreover, Japanese Patent No. 2953200 discloses a material system usinga combination of an inorganic material network and a photopolymerizablemonomer. When an inorganic material capable of forming the network isused as a binder, there are produced advantages that this materialsystem is superior in heat resistance, environmental resistance andmechanical strength and further the refractive index difference betweenthe photopolymerizable organic monomer and the inorganic material can bemade larger. But there are caused problems that the hologram recordingfilm prepared from this material system is somewhat brittle and inferiorin properties of flexibility, processability and coating ability andthat it is difficult to prepare a homogenous coating material since thecompatibility between the inorganic binder and the organic monomer isnot good.

Japanese Patent Application National Publication No. 2000-508783discloses, as a hologram recording material, a material in which metalsuperfine particles are dispersed in a solid matrix. However, in thismaterial, it is required to provide the matrix with fluidity so thatthere is a problem of poor solidity.

In particular, known examples of a combination use of a high refractiveindex binder resin containing an aromatic ring and a low refractiveindex fluorine-contained monomer include Japanese Patent ApplicationLaid-Open (JP-A) No. 5-210343, 5-210344 and 5-257416. According to thiscombination, however, the sensitivity at the time of hologram-exposureis not so high since the polymerization reactivity is insufficient. Inorder to promote the polymerizability of the fluorine-contained monomer,it is stated that a polyfunctional acrylate is added thereto. However,this method obstructs the low refractivity which the fluorine-containedmonomer originally has.

A known example of a combination use of a low refractive index binderresin, composed of a fluorine-contained acrylic monomer and anonfluorine-contained acrylic monomer, and a high refractive indexmonomer in which an aromatic ring is contained include JP-A No. 6-67588.However, this example also has problems that the low refractivity of thefluorine-contained acrylic monomer is obstruct by copolymerizationthereof with the nonfluorine-contained acrylic monomer and furtheryellowing is liable to be caused by the aromatic ring of the aromaticring-contained monomer.

Since fluorine-contained compounds generally have a very low refractiveindex, they are expected as materials for making a refractive indexmodulation (Δn) large. However, the compounds are poor in compatibilitywith other blend components such as a binder resin. Thus, the range fromwhich other blend components can be selected is limited and further itis difficult to make the blend ratio of the fluorine-contained compoundhigh. For this reason, in material systems in which a fluorine-containedcompound is blended as a refractive index modulating component, the Δnthereof has been hitherto unable to be sufficiently improved. Thus, ithas been desired to improve the Δn when such a material is applied tonew optical elements.

SUMMARY OF THE INVENTION

In light of the above-mentioned situation, the present invention hasbeen achieved. An object of the present invention is to provide a volumehologram recording material, a volume hologram recording medium, and avolume hologram which have a larger refractive index modulation (Δn)than those in the prior art.

In order to attain the above-mentioned object, the volume hologramrecording photosensitive composition provided by the present inventionis characterized in that it comprises a fluorine-contained photoreactivecompound represented by the following formula (1):R¹—R³—(CF₂)n-R⁴—R²  Formula (1)wherein R¹ and R² are photoreactive groups which can be bonded to eachother by photoreaction, and each of R³ and R⁴ is independently a singlebond or a bivalent hydrocarbon group having 1 to 5 carbon atoms, and nis an integer of 1 or more.

The volume hologram recording photosensitive medium provided by thepresent invention is characterized in that it has a hologram recordingsection made of the above-mentioned volume hologram recordingphotosensitive composition.

The volume hologram provided by the present invention is characterizedin that it has a hologram layer which is formed by exposing, to light, ahologram recording section made of the above-mentioned volume hologramrecording photosensitive composition, the refractive index modulation(Δn) between its low refractive index region and its high refractiveindex region being 0.016 or more.

The volume hologram recording photosensitive composition according tothe present invention comprises the fluorine-contained photoreactivecompound represented by the formula (1) as a refractive index modulatingcomponent. This fluorine-contained photoreactive compound has fluorineatoms in the molecular structure thereof; therefore, the compoundgenerally has a very small refractive index and is suitable for a lowrefractive index type refractive index modulating component.

Since this fluorine-contained photoreactive compound has a very highcompatibility with other blend components such as a binder, ranges fromwhich other blend components can be selected extend very wide.Accordingly, binder resins, monomers and oligomers which take a largerefractive index modulation can be selected from wide ranges. Thus, theblend ratio of the fluorine-contained photoreactive compound in thevolume hologram recording photosensitive composition can be made highwithout damaging the transparency of the composition.

Since this fluorine-contained photoreactive compound has twophotopolymerizable groups in the single molecule, it has a largepolymerization reactivity at the time of hologram-exposure.

Consequently, use of the fluorine-contained photoreactive compoundrepresented by the formula (1) provides a volume hologram recordingphotosensitive composition, a volume hologram recording medium and avolume hologram which are superior in hologram recording performancessuch as a refractive index modulation and sensitivity.

The photoreactive groups R¹ and R² contained in the fluorine-containedphotoreactive compound represented by the formula (1) preferably haveany one photoreactivity selected from the group consisting of theradical photopolymerization, cationic photopolymerization, anionicphotopolymerization and polymerization advancing via photodimerization.It is particularly preferable that the photoreactive groups R¹ and R²are an acryloyl group or a methacryloyl group independently to each oran epoxy group or an oxetanyl group independently to each.

Among the fluorine-contained photoreactive compounds represented by theformula (1), preferred are compounds wherein each of R¹ and R² is anepoxy group and a compound wherein each of R¹ and R² is an oxetanylgroup represented by the following formula (2):

wherein R⁵ is a hydrogen atom or an alkyl group having 1 to 10 carbonatoms.

It is also preferable that R³ and R⁴ are a single bond or a linearhydrocarbon group having 1 to 5 carbon atoms independently to eachother.

The fluorine-contained photoreactive compound represented by the formula(1) exhibit superior compatibility with various binder resins. As thebinder resin, it is preferable to use at least one selected from thegroup consisting of a thermoplastic resin, a thermosetting resin, anorganic-inorganic hybrid polymer, and an organic metal compoundrepresented by the formula (4):M′(OR″)n′  Formula (4)wherein M′ represents a metal such as Ti, Zr, Zn, In, Sn, Al or Se, andR″ represents an alkyl group having 1 to 10 carbon atoms, and n′ is thevalence number of the metal M′.

The volume hologram recording photosensitive composition according tothe present invention can comprise a second refractive index modulatingcomponent other than the fluorine-contained photoreactive compoundrepresented by the formula (1). When the fluorine-containedphotoreactive compound represented by the formula (1) is used incombination with the second refractive index modulating component, therefractive index modulation Δn at the time of hologram-exposure can bemade larger by the so-called volume exclusion effect.

Also, by adding metal fine particles having a refractive index differentfrom that of the fluorine-contained photoreactive compound representedby the formula (1) to the volume hologram recording photosensitivecomposition, the volume exclusion effect can be obtained in the samemanner as in the case of the addition of the second refractive indexmodulating component. Consequently, the refractive index modulation Δncan be made large.

When a sensitizing dye is used, particularly high transparency can beobtained by adding a sensitizing dye which is made transparent byheating or irradiation with ultraviolet rays, thus being preferable.

BRIEF DESCRIPTION OF THE DRAWINGS

In the accompanying drawings:

FIG. 1 is a schematic sectional view illustrating one example of ahologram transfer foil according to the present invention,

FIG. 2 is an explanatory view of an example of transferring operationwith the use of the hologram transfer foil, and

FIG. 3 is a graph showing a method for calculating diffractionefficiency.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

The present invention is described in detail hereinafter. In thespecification, the word “meth(acrylate)” represents acrylate andmethacrylate, the word “meth(acryl)” represents acryl and methacryl, andthe word “meth(acryloyl)” represents acryloyl and methacryloyl.

The volume hologram recording photosensitive composition providedaccording to the present invention contains at least afluorine-contained photoreactive compound represented by the followingformula (1):R¹—R³—(CF₂)n-R⁴—R²  Formula (1)wherein R¹ and R² are photoreactive groups which can be bonded to eachother by photoreaction, and each of R³ and R⁴ is independently a singlebond or a bivalent hydrocarbon group having 1 to 5 carbon atoms, and nis an integer of 1 or more.

The value Δn calculated on the basis of Kogelnik's theory is a valuerepresenting a refractive index modulation in a refractive indexdistribution formed in accordance with interference light (that is,light in which interference fringes are generated) incident on aphotosensitive material. As this value Δn is larger, abetter hologram,which is visually brighter, can be obtained.

The volume hologram recording photosensitive composition according tothe present invention contains, as a component for generating thisrefractive index modulation Δn (a refractive index modulatingcomponent), a bifunctional fluorine-contained photoreactive compoundhaving a structure represented by the formula (1). Thisfluorine-contained photoreactive compound has fluorine atoms in themolecular structure thereof, and therefore, generally has a very smallrefractive index, thus being suitable for a refractive index modulatingcomponent of a low refractive index type. The fluorine-containedphotoreactive compound contained in a volume hologram recording materiallayer formed by using the volume hologram recording photosensitivecomposition of the present invention diffuse and move at the time ofhologram-exposure, thereby being unevenly present at a highconcentration at intensely-exposed regions or weakly-exposed regions.Then the molecules are fixed by polymerization reaction, so that therefractive index of the regions where the fluorine-containedphotoreactive compounds are unevenly present is remarkably lowered.

Since the fluorine-contained photoreactive compound having the structurerepresented by the general formula (1) has a very high compatibilitywith other blend components such as a binder resin, ranges from whichother blend components can be selected extend wide. Accordingly, thebinder resins, monomers and oligomers which take a large refractiveindex modulation can be selected from wide ranges. Thus, the blend ratioof the fluorine-contained photoreactive compound in the volume hologramrecording photosensitive composition can be made high without damagingthe transparency of the composition.

Since this fluorine-contained photoreactive compound has twophotopolymerizable groups in the single molecule thereof, thepolymerization reactivity thereof is large at the time ofhologram-exposure. This fluorine-contained photoreactive compound has alarge polymerization reactivity, and it is unnecessary to add a largeamount of a polyfunctional acrylate or the like for raising thepolymerizability of a fluorine-contained monomer as performed in theprior art. Therefore, low refractivity, which is a characteristic of thefluorine-contained photoreactive compound, is not obstructed.

Consequently, this fluorine-contained photoreactive compound is superiorin compatibility and polymerization reactivity, and by incorporatingthis compound, as a refractive index modulating component, into a volumehologram recording photosensitive composition, superior sensitivity andrefractive index modulating effect can be obtained.

In the formula (1), R¹ and R² may be the same or different if they arephotoreactive groups (atoms or atomic groups which have photoreactivity)which can be bonded to each other by irradiation with light. Examples ofthe photoreactive group include groups

Which advance reaction with a reaction style of polymerization such asradical photopolymerization, cationic photopolymerization or anionicphotopolymerization, or polymerization advancing via photodimerizationor the like.

Examples of the radical photopolymerizable group include functionalgroups having an ethylenically unsaturated bond (preferably, anethylenic double bond). Specific examples thereof include acryloyl,methacryloyl, vinyl, vinylcycloalkyl, and allyl groups or the like.Among these groups, acryloyl and methacryloyl groups are preferable fromthe viewpoint of reactivity.

Examples of the cationic photopolymerizable group include cyclic ethergroups such as epoxy and oxetanyl groups; thioether groups; and vinylether groups. Among these groups, cyclic ether groups such as epoxy andoxetanyl groups are preferred since the shrinkage of cured product,following the polymerization reaction thereof, is small. Compoundshaving an epoxy group among cyclic ether groups have an advantage thatcompounds having various structures are easily available. An oxetanylgroup among cyclic ether groups has advantages that it has a higherpolymerization degree and a lower toxicity than an epoxy group.

An example of the fluorine-contained photoreactive compound wherein R¹and R² in the formula (1) are epoxy groups is a compound represented bythe following formula (1a):

wherein n is preferably an integer of 4 to 20.

As the fluorine-contained photoreactive compound wherein R¹ and R² inthe formula (1) are oxetanyl groups, there is preferably used a compoundwherein each of R¹ and R² has an oxetanyl group represented by thefollowing formula (2):

wherein R⁵ is a hydrogen atom or an alkyl group having 1 to 10 carbonatoms.

More specifically, there can be used a compound represented by thefollowing formula (1b):

wherein R⁵ is the same as described above, and n is preferably from 4 to20.

Examples of the anionic photopolymerization-reactive group include avinyl group having an electron withdrawing group, cyclic ether groups,such as epoxy and oxetanyl groups, which are also the above-mentionedcationic photopolymerizable groups, cyclic urethane groups, cyclicureas, and cyclic siloxane groups.

An example of the polymerization-reactive group based onphotodimerization requiring no initiator is a vinyl cinnamate group. Itis also possible to use a relationship between a donating group and anaccepting group whose reaction advances at a ratio of 1:1. An example ofthe donating group is a maleimide group, and an example of the acceptinggroup is a vinyl ether group. In this case, it is advisable that acompound wherein R¹ and R² are donating groups and a compound wherein R¹and R² are accepting groups are mixed at a ratio of 1:1, and the mixtureis used.

Specific examples of the combination of R¹ and R² which can be bonded toeach other and are different from each other include a combination of anacryloyl group and a methacryloyl group, and a combination of an epoxygroup and an oxetanyl group.

R³ and R⁴ are a single bond or a bivalent hydrocarbon group having 1 to5 carbon atoms independently to each other. It should be noted that acase in which repeating units of a methylene fluoride group (CF₂) arebonded directly (that is, bonded through single bonds) to R¹ and R² isalso included in the definition of R³ and R⁴. R³ and R⁴ which arehydrocarbon groups may be linear hydrocarbon groups or hydrocarbongroups having a side chain. R³ and R⁴ are preferably linear hydrocarbongroups or single bonds. Specific examples of the hydrocarbon groupinclude methylene, ethylene, trimethylene, tetramethylene and propyleneor the like. Methylene is preferable in order to make the refractiveindex as low as possible.

The number n of the repeating units of the methylene fluoride group(CF₂) is preferably from 1 to 30 from the viewpoint of diffusing/movingability, and is more preferably from 4 to 20, most preferably from 4 to10 from the viewpoint of volatilization and safety as well as thediffusing/moving ability.

The method for synthesizing the fluorine-contained photoreactivecompound represented by the formula (1) may be, for example, a method ofderiving this compound from fluorinated diiodo alkane. In a case whereeach of R¹ and R² is an epoxy group and n is 4, if the known method, forexample a synthesis method according to a method described in, forexample, Japanese Patent Application Publication (JP-B) No. 54-11284,JP-B 59-22712 or JP-B 6-60116, or J. Fluorine Chem., 73, 151 (1995) orthe like is performed by using octafluoro-1,4-diiodobutane (trade name:I-8407, manufactured by Daikin Industries, Ltd.) as the startingmaterial, the fluorine-contained photoreactive compound can besynthesized via a diol derivative from the starting material.

In a case where each of R¹ and R² is an oxetanyl group, if theabove-mentioned dial derivative is converted to an alkali metalalcoholate and further the alcoholate is reacted with a sulfonate of a3-hydroxymethyloxetanes, referring to a known method, for example, amethod described in JP-A No. 2000-336082, the fluorine-containedphotoreactive compound can be synthesized.

The volume hologram recording photosensitive composition according tothe present invention may be incorporate with the other components suchas a photopolymerization initiator, a binder resin, a sensitizing dye, arefractive index modulating component other than the fluorine-containedphotoreactive compound (i.e., a second refractive index modulatingcomponent) or the like together with the fluorine-containedphotoreactive compound having a chemical structure of the formula (1)described above, as required.

It is preferable to incorporate, into the volume hologram recordingphotosensitive composition according to the present invention, aphotopolymerization initiator for initiating or promoting polymerizationor dimerization reaction of the fluorine-contained photoreactivecompound by hologram-exposure. The photopolymerization initiator isappropriately selected from a radical photopolymerization initiator, acationic photopolymerization initiator, an anionic photopolymerizationinitiator, and other initiators in accordance with the style of thephotoreaction, and then used.

Examples of the radical photopolymerization initiator include imidazolederivatives, bisimidazole derivatives, N-arylglycine derivatives,organic azide compounds, titanocenes, aluminate complexes, organicperoxides, N-alkoxypyridinium salts, and thioxanthone derivatives.Specific examples thereof include1,3-di(tert-butyldioxycarbonyl)benzophenone,3,3′,4,4′-tetrakis(tert-butyldioxycarbonyl)benzophenone,3-phenyl-5-isooxazolone, 2-mercaptobenzimidazole,bis(2,4,5-triphenylimidazole). 2,2-dimethoxy-1,2-diphenylethane-1-one(trade name: Irgacure 651, manufactured by Ciba Specialty Chemicals,inc.), 1-hydroxy-cyclohexyl-phenyl-ketone (trade name: Irgacure 184,manufactured by Ciba Specialty Chemicals, inc.),2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butane-1-one (tradename: Irgacure 369, manufactured by Ciba Specialty Chemicals, inc.), andbis(η⁵-2,4-cyclopentadiene-1-yl)-bis(2,6-difluoro-3-(1H-pyrrole-1-yl)-phenyl)titanium)(trade name: Irgacure 784, manufactured by Ciba Specialty Chemicals,inc). However, it is not limited to these examples.

Examples of the cationic photopolymerization initiator includesulfonates, imidesulfonate, dialkyl-4-hydroxysulfonium salts,p-nitrobenzylarylsulfonate, silanol-aluminum complexes, and (η⁶-benzene)(η⁵-cyclopentadienyl)iron (II). Specific examples thereof includebenzoin tosylate, 2,5-dinitrobenzyl tosylate, and N-tosylphthalicimide.However, it is not limited to these examples.

Examples of a compound which can be used as either of the radicalphotopolymerization initiator or the cationic photopolymerizationinitiator include aromatic iodonium salts, aromatic sulfonium salts,aromatic diazonium salts, aromatic phosphonium salts, triazinecompounds, and iron arene complexes. Specific examples thereof include:iodonium salts of chloride, bromide, borofluoride, hexafluorophosphate,hexafluoroantimonate or the like of iodoniums such as diphenyliodonium,ditolyliodonium, bis(p-tert-butylphenyl)iodonium andbis(p-chlorophenyl)iodonium, sulfonium salts of chloride, bromide,borofluoride, hexafluorophosphate, fluoroantimonate or the like ofsulfonates such as triphenylsulfonium, 4-tert-butyltriphenylsulfoniumand tris(4-methylphenyl)sulfonium, and 2,4,6-substituted-1,3,5-triazinecompounds such as 2,4,6-tris(trichloromethyl)-1,3,5-triazine,2-phenyl-4,6-bis(trichloromethyl)-1,3,5-triazine and2-methyl-4,6-bis(trichloromethyl)-1,3,5-triazineorthe like. However, itis not limited to these examples.

Examples of the anionic photopolymerization initiator include compoundswhich generate amine by irradiation with, for instance, ultravioletrays. Specific examples thereof include 1,10-diaminodecane,4,4′-trimethylenedipiperidine, carbomates and derivatives thereof,cobalt-amine complexes, aminooxyiminos, and ammonium borates or thelike. Example of a product commercially available is NBC-101manufactured by Midori Kagaku Co., Ltd.

The photopolymerization initiator is preferably subjected todecomposition treatment after hologram recording from a viewpoint of astabilization of the recorded hologram. For example, the initiator of anorganic peroxide type is easily decomposed by irradiation withultraviolet rays, thus being preferable.

By incorporating a binder resin into the volume hologram recordingphotosensitive composition according to the present invention, anon-fluid volume hologram recording layer can be formed on a substrate,and it is accordingly used as a dry-developable hologram formingmaterial.

The fluorine-contained photoreactive compound having the structurerepresented by the formula (1) makes it possible to produce a hologramby itself without other components such as the binder resin beingincorporated. In this case, however, the fluidity of this compound istoo high, and it is therefore necessary that a proper method, forexample a method to put the fluorine-contained photoreactive compoundair-tightly between transparent substrates such as glass is applied toform a photosensitive composition layer consisting of only said compoundor consisting essentially of said compound, and then a hologram-exposureis carried out.

The fluorine-contained photoreactive compound represented by the formula(1) exhibits superior compatibility with various binder resins. Forexample, ordinary thermoplastic resins, oligomer type setting resins,organic-inorganic hybrid resins, and so on can be used. Thefluorine-contained photoreactive compound is a low refractive index typerefractive indexmodulating component, and therefore, in order to makethe refractive index modulation (Δn) after hologram-exposure large, itis preferred to use a binder resin having a large refractive index. Thebinder resin may have polymerization reactivity or have nopolymerization reactivity. In a case where the binder resin haspolymerization reactivity, a volume hologram recording photosensitivemedium or a volume hologram using the volume hologram recordingphotosensitive composition according to the present invention isimproved in the membrane physical properties (physical properties of acoating layer) such as strength and heat resistance or the like, wherebybeing preferable.

As the binder resin, a thermoplastic resin can be used. Specifically,there may be used poly(meth)acrylate or partially-hydrolyzed productsthereof, polyvinyl acetate or hydrolyzed products thereof, polyvinylalcohol or partially-acetalized products thereof, triacetylcellulose,polyisoprene, polybutadiene, polychloroprene, silicone rubber,polystyrene, polyvinyl butyral, polyvinyl chloride, polyarylate,chlorinated polyethylene, chlorinated polypropylene,poly-N-vinylcarbazole or derivatives thereof, poly-N-vinylpyrrolidone orits derivatives, copolymer of styrene and maleic anhydride orsemi-esterifiedproducts thereof, copolymers which contain, as acomponent to be copolymerized, at least one selected fromcopolymerizable monomers such as acrylic acid, acrylic esters,acrylamide, acrylonitrile, ethylene, propylene, vinyl chloride, vinylacetate or the like, or mixture thereof.

As the binder resin, it is also possible to use an oligomer type settingresin. Examples thereof include epoxy compounds produced by condensationreaction of any one of various phenolic compounds such as bisphenol A,bisphenol S, Novolak, o-cresol Novolak, p-alkylphenol Novolak or thelike and epichlorohydrin.

As the binder resin, an organic-inorganic hybrid resin using sol-gelreaction can also be used. The organic-inorganic hybrid resin usingsol-gel reaction is any resin which can be condensation-polymerized bysol-gel reaction or has already been condensation-polymerized by sol-gelreaction, and which is capable of providing, after being subjected tothe sol-gel reaction, a polymer structure in which organic structuremoieties and inorganic structure moieties are coincidentally present.

An example of the organic-inorganic hybrid resin is an organic-inorganichybrid polymer, such as a copolymer of a vinyl monomer and an organicmetal compound having a polymerizable group represented by the followingformula (3):RmM(OR′)n  Formula (3)wherein M represents a metal such as Si, Ti, Zr, Zn, In, Sn, Al or Se, Rrepresents a vinyl group having 1 to 10 carbon atoms, or a(meth)acryloyl group, R′ represents an alkyl group having 1 to 10 carbonatoms, and m+n is the valence number of the metal M.

Examples of the compound wherein the metal atom M is Si includevinyltriethoxysilane, vinylmethoxysilane, vinyltributoxysilane,vinyltriallyloxysilane, vinyltetraethoxysilane, vinyltetramethoxysilane,and (meth)acryloxypropyltrimethoxysilane and so on.

Examples of the vinylmonomer used in the organic-inorganic hybridpolymer include (meth)acrylic acid and (meth)acrylates. However, theyare not limited to these examples.

Among the organic-inorganic hybrid resins, an organic metal compoundrepresented by a formula (4) described below is particularly effectivefor making the refractive index difference between the binder resin andthe fluorine-contained photoreactive compound larger since the organicmetal compound has a smaller molecular weight and a large effect ofraising the crosslink density in comparison with the above-mentionedorganic-inorganic hybrid polymer which has already been polymerized:M′(OR″)n′  Formula (4)wherein M′ represents a metal such as Ti, Zr, Zn, In, Sn, Al or Se, R″represents an alkyl group having 1 to 10 carbon atoms, and n′ is thevalence number of the metal M.

When the organic metal compound represented by the formula (4) is addedto the volume hologram recording photosensitive composition, thecompound associates with the above-mentioned binder resin to form anetwork structure through sol-gel reaction in the presence of water andan acid catalyst, whereby providing effects of improving toughness orheat resistance of the resultant layer as well as raising of therefractive index of the binder. In order to raise the refractive indexdifference between the binder resin and the fluorine-containedphotoreactive compound, it is preferable to use, as the metal M′, onehaving a refractive index being as high as possible.

It is more preferable to use, as the binder resin, a binder resin whichcan form a covalent bond with the photoreactive group of thefluorine-contained photoreactive compound. In this case, if unreactedmolecules of the fluorine-contained photoreactive compound or polymermolecules of the fluorine-contained photoreactive compound afterhologram-exposure are covalent-bonded to the binder resin molecules in agiven reaction style, a stable bond between the fluorine-containedphotoreactive compound and the binder resin can be generated, therebyobtaining a hologram layer superior in layer strength, heat resistance,hologram-fixing property and so on.

It is preferable to introduce a functional group which is photoreactivewith or thermally-polymerizable with the photoreactive group of thefluorine-contained photoreactive compound, as a functional group capableof forming the above-mentioned covalent bond, into the binder resin. Anyhologram recording material layer of a photopolymer type is frequentlysubjected to exposuring or heating homogenous over the entire surfacethereof in order to promote the variation in the refractive index orcomplete the polymerization reaction after the process ofhologram-exposure. In a case where the functional group of the binderresin is photopolymerizable or thermally polymerizable with thephotopolymerizable group of the fluorine-contained photoreactivecompound, the following two processes can be unified to one process in acommon reaction style: the process of exposing or heating the wholesurface of a layer made of the hologram recording photosensitivecomposition (hereinafter referred to as “a hologram recording materiallayer”) in order to promote the variation in the refractive index or fixa hologram after hologram-exposure and the process of copolymerizing thebinder resin with the fluorine-contained photoreactive compound or apolymer thereof in order to improve the membrane strength or theendurance of the hologram recording material layer, thus beingpreferable.

It is particularly preferable to introduce a functional groupphotopolymerizable with the photoreactive group of thefluorine-contained photoreactive compound into the binder resin. Forexample, when the fluorine-contained photoreactive compound has, as itsphotoreactive group, an ethylenically unsaturated group capable ofcausing addition polymerization reaction, a binder resin having asimilar ethylenically unsaturated bond (preferably, an ethylenic doublebond) capable of causing additional polymerization, such as an acryloylgroup or a methacryloyl group is used. When the fluorine-containedphotoreactive compound has a cationic photopolymerizable group such asan epoxy group, a binder resin having a functional group polymerizablewith the cationic photopolymerizable group at the time ofhologram-exposure is used. Examples of the functional grouppolymerizable with the cationic photopolymerizable group at the time ofhologram-exposure include functional groups such as hydroxyl andcarboxylic groups as well as cationic photopolymerizable groupsthemselves, such as epoxy and vinyl ether groups.

In a case where the above-mentioned particularly preferable combinationis adopted and when the hologram recording material layer is subjectedto hologram-exposure, the fluorine-contained photoreactive compounds inintensely exposed regions are polymerized not only with otherfluorine-contained photoreactive compounds being adjacent but also withthe surrounding the binder resin, and reactivity accordingly becomeshigh, thereby providing effect of improving the sensitivity at the timeof the hologram-exposure and the refractive index modulation. Also inthis case, if ordinary exposuring or heating homogenous over the entiresurface is carried out after the hologram-exposure, the variation in therefractive index is promoted and the polymerization reaction iscompleted to form a hologram, and further the formation of the covalentbond between the binder resin and the fluorine-contained photoreactivecompound is further advanced so as to provide an advantageous effectthat superior layer physical properties such as layer strength and heatresistance is give to the hologram recording material layer.

As the binder resin, only one may be selected from the materialsexemplified above to be used, or two or more may be mixed to be used.

When the hologram recording material comprising two or more refractiveindex modulating components having different refractive indexes andphotopolymerization rates is subjected to hologram-exposure,polymerization reaction of the refractive index modulating componenthaving a higher polymerization rate advances preferentially in intenselyexposed regions so that the concentration of the high polymerizationrate refractive index modulating component rises. At the same time, thelow polymerization rate refractive index modulating component is drivenout from the intensely exposed regions to be diffused and moved toweakly-exposed regions and polymerized and fixed therein. As a result, arefractive index difference between the intensely exposed regions andthe weakly-exposed regions is generated on the basis of the respectiverefractive indexes of the different kinds of refractive index modulatingcomponents. This is volume exclusion effect.

In order to make the refractive index modulation Δn large by such volumeexclusion effect, it is allowable to incorporate, into the volumehologram recording photosensitive material of the present invention, asecond refractive index modulating component having a refractive indexdifferent from that of the fluorine-contained photoreactive compoundrepresented by the formula (1) and having a polymerization ratedifferent from that of the fluorine-contained photoreactive compound.

The fluorine-contained photoreactive compound represented by the formula(1) is a low refractive index type refractive index modulating componentand the second refractive index modulating component is a highrefractive index type refractive index modulating component in usual.Therefore, when the polymerization rate of the fluorine-containedphotoreactive compound represented by the formula (1) is larger thanthat of the second refractive index modulating component, thefluorine-contained photoreactive compounds diffuse and move to theintensely exposed regions to concentrate and cause lowering of therefractive index in usual, while the second refractive index modulatingcomponents are driven out from the intensely exposed regions to bediffused and moved to the weakly-exposed regions to concentrate andcause rising of the refractive index in usual. On the other hand, whenthe polymerization rate of the fluorine-contained photoreactive compoundrepresented by the formula (1) is lower than that of the secondrefractive index modulating component, the converse to theabove-mentioned case is caused. That is, a refractive index usuallybecomes high in the intensely exposed regions by rising concentration ofthe second refractive index modulating component, and a refractive indexusually becomes low in the weakly-exposed regions by risingconcentration of fluorine-contained photoreactive compound.

As the second refractive index modulating component, there can be used acompound which can undergo the advance of polymerization or dimerizationby irradiation with light and can diffuse and move in the volumehologram recording material layer (provided that the fluorine-containedphotoreactive compound represented by the formula (1) is excluded).Examples thereof include compounds which can undergo the advance ofpolymerization in a reaction style such as radical photopolymerization,cationic photopolymerization, anionic photopolymerization, orpolymerization via photodimerization. About the second refractive indexmodulating component, differences of the refractive index and thepolymerization rate thereof from those of the fluorine-containedphotoreactive compound represented by the formula (1) are preferablymade as large as possible.

The second refractive index modulating component is a component forenlarging the refractive index modulation Δn generated by the refractiveindex difference between the fluorine-contained photoreactive compoundrepresented by the formula (1) and the binder resin. For this reason, asthe second refractive index modulating component, selected is acomponent satisfying a largeness and smallness relationship having thesame tendency as the largeness and smallness relationship between therefractive index of the fluorine-contained photoreactive compound andthat of the binder resin. In other words, the fluorine-containedphotoreactive compound is generally a low refractive index typerefractive index modulating component, and therefore, a binder resinhaving a high refractive index is usually combined with thefluorine-contained photoreactive compound, and further as the secondrefractive index modulating component, there is used a high refractiveindex type refractive index modulating component (that is, a refractiveindex modulating component which is unevenly located and polymerized inthe intensely exposed regions or weakly-exposed regions so as to makethe refractive index of the regions high) like the binder resin.

If the second refractive index modulating component has a polymerizationrate different from that of the fluorine-contained photoreactivecompound represented by the formula (1), the reaction styles of the twomay be the same, for example, as when the two are radicalphotopolymerizable, or may be different, for example, as when onethereof is radical photopolymerizable and the other is cationicphotopolymerizable.

As the second refractive index modulating component, an oligomer or apolymer containing a photoreactive group may be used. It is howeverpreferable to use a monomer containing a photoreactive and bondablegroup since the refractive index modulating component diffuse and movemore easily in the hologram recording material layer at the time ofhologram-exposure as the molecular weight thereof is smaller.

The radical photopolymerizable compound out of the second refractiveindex modulating component may be a compound having at least oneethylenically unsaturated bond capable of being addition-polymerized.Examples thereof include unsaturated carboxylic acid and salts thereof,esters of unsaturated carboxylic acid and aliphatic polyvalent alcohol,and amide compounds of unsaturated carboxylic acid and aliphaticpolyvalent amine compound. Specific examples of monomer of the ester ofunsaturated carboxylic acid and aliphatic polyvalent alcohol includeethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate,1,3-butanediol di(meth)acrylate, tetramethylene glycol di(meth)acrylate,propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate,trimethylolpropane tri(meth)acrylate, trimethylolpropanetri((meth)acryloyloxypropyl)ether, trimethylolethane tri(meth)acrylate,hexanediol di(meth)acrylate, 1,4-cyclohexanediol di(meth)acrylate,tetraethylene glycol di(meth)acrylate, pentaerythritol di(meth)acrylate,pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate,dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate,dipentaerythritol tetra(meth)acrylate, dipentaerythritolhexa(meth)acrylate, sorbitol tri(meth)acrylate, sorbitoltetra(meth)acrylate, sorbitol penta(meth)acrylate, sorbitolhexa(meth)acrylate, tri((meth)acryloyloxyethyl)isocyanurate,polyester(meth)acrylate oligomer, 2-phenoxyethyl(meth)acrylate,phenolethoxylate mono(meth)acrylate,2-(p-chlorophenoxy)ethyl(meth)acrylate, p-chlorophenyl(meth)acrylate,phenyl(meth)acrylate, 2-phenylethyl(meth)acrylate,(2-(meth)acryloxyethyl)ether of bisphenol A, ethoxidized bisphenol Adiacrylate, 2-(1-naphthyloxy)ethyl(meth)acrylate, o-biphenyl acrylate,9,9-bis(4-(meth)acryloxydiethoxyphenyl)fluorene,9,9-bis(4-(meth)acryloxytriethoxyphenyl)fluorene,9,9-bis(4-acryloxydipropoxyphenyl)fluorene,9,9-bis(4-acryloxyethoxy-3-methylphenyl)fluorene,9,9-bis(4-acryloxyethoxy-3-ethylphenyl)fluorene, and9,9-bis(4-acryloxyethoxy-3,5-dimethyl)fluorene or the like.Sulfur-contained acryl compounds disclosed in JP-A No. 61-72748 can alsobe used. Examples thereof include4,4′-bis(β-(meth)acryloyloxyethylthio)diphenylsulfone,4,4′-bis(β-(meth)acryloyloxyethylthio)diphenyl ketone,4,4′-bis(β-(meth)acryloyloxyethylthio)-3,3′,5,5′-tetrabromodiphenylketone, 2,4-bis(β-(meth)acryloyloxyethylthio)dipenyl ketone. However,acryl compounds which can be used are not limited to these examples.

Examples of the cationic photopolymerizable compound out of the secondrefractive index modulating component include cyclic ethers such asepoxy and oxetanyl rings, thioethers and vinyl ethers. Specific examplesof the epoxy ring contained compound include polyalkylene glycoldiglycidyl ether, bisphenol A diglycidyl ether, glycerin triglycidylether, diglycerol triglycidyl ether, diglycidyl hexahydrophthalate,trimethylolpropane diglycidyl ether, allyl glycidyl ether, phenylglycidyl ether, and cyclohexene oxide. However, the epoxy ring containedcompound is not limited to these examples.

As the anionic photopolymerizable compound out of the second refractiveindex modulating components, a vinyl monomer having an electronwithdrawing property, that is, a monomer having an electron withdrawinggroup and an ethylenic double bond whose anionic polymerization activityis made high by the electron withdrawing group can be used. Examples ofsuch a monomer include styrene, methyl α-cyanoacrylate, methyl vinylketone, and acrylonitrile. As the anionic polymerizable compound, therecan be appropriately used a monomer having a chemical structure capableof undergoing ring-opening polymerization by an anionic catalyst, suchas a cyclic ether, a lactone, a lactam, a cyclic urethane, a cyclicurea, or a cyclic siloxane.

By combining the fluorine-contained photoreactive compound representedby the formula (1) with a proper binder resin and/or a proper secondrefractive index modulating component, the refractive index modulation(Δn) after hologram-exposure can be made larger. Specific examples of aneffective combination of materials for generating a refractive indexdifference inside interference fringes include the following:

-   (1) a combination comprising the fluorine-contained photosensitive    compound represented by the formula (1), a binder resin having a    refractive index different from that of the fluorine-contained    photosensitive compound, and a radical photopolymerizable compound    which is the second refractive index modulating component having a    refractive index different from that of the fluorine-contained    photosensitive compound;-   (2) a combination comprising the fluorine-contained photosensitive    compound represented by the formula (1), a binder resin having a    refractive index different from that of the fluorine-contained    photosensitive compound, and a cationic photopolymerizable compound    which is the second refractive index modulating component having a    refractive index different from that of the fluorine-contained    photosensitive compound;-   (3) a combination comprising the fluorine-contained photosensitive    compound represented by the formula (1), and two or more radical    photopolymerizable compounds which are the second refractive index    modulating components each having a refractive index different from    that of the fluorine-contained photosensitive compound; and-   (4) a combination comprising the fluorine-contained photosensitive    compound represented by the formula (1), a radical    photopolymerizable compound which is the second refractive index    modulating component having a refractive index different from that    of the fluorine-contained photosensitive compound, and a cationic    photopolymerizable compound which is the second refractive index    modulating component having a refractive index different from that    of the fluorine-contained photosensitive compound.

In order to make the refractive index modulation Δn large by volumeexclusion effect, it is also allowable to incorporate, into the volumehologram recording photosensitive composition of the present invention,metal fine particles having a refractive index different from that ofthe fluorine-contained photoreactive compound represented by the formula(1).

If the metal fine particles can diffuse and move in the volume hologlamrecording material layer and have a refractive index different from thatof the fluorine-contained photoreactive compound represented by theformula (1), the particles may be non-reactive metal fine particles orpolymerization-reactive metal fine particles having surfaces onto whichphotopolymerization-reactive groups or other reactive groups areintroduced.

About the metal fine particles, the difference of the refractive indexthereof from the refractive index of the fluorine-containedphotoreactive compound represented by the formula (1) is preferably madeas large as possible. As the metal fine particles, selected is onesatisfying a largeness and smallness relationship having the sametendency as the largeness and smallness relationship between therefractive index of the fluorine-contained photoreactive compound andthat of the binder resin similarly to the second refractive indexmodulating component. From the viewpoint of diffusing/moving ability inthe volume hologram recording material layer, the particle size of themetal fine particles is preferably not more than the wavelength forhologram recording. Specifically, the particle size is preferably from 1to 700 nm, more preferably from 5 to 500 nm. The non-photopolymerizablemetal fine particles are made of titania, zirconia, zinc, indium, tin orthe like.

When the hologram recording material comprising the metal fine particleshaving a refractive index different from that of the fluorine-containedphotoreactive compound represented by the formula (1) is subjected tohologram-exposure, a refractive index difference is generated by adifference in photoreactivity between the fluorine-containedphotoreactive compound and the metal oxide in accordance with amechanism similar to that in the case of the hologram recording materialcomprising the second refractive index modulating component.

The method for introducing a photopolymerization-reactive group onto themetal fine particles may be a method of using a coupling agent havingphotopolymerization reactivity to conduct surface treatment in a drymanner, a wet manner, a blend manner or some other manner, whereby thesurfaces of the metal fine particles are subjected to couplingtreatment. Examples of the metal fine particles onto which thephotopolymerization-reactive group is introduced include titania,zirconia, zinc, indium, and tin or the like, as described above. Thephotopolymerization-reactive group to be introduced may be apolymerization-reactive group such as one contained in the secondrefractive index modulating component, that is, a group which canundergo the advance of polymerization in a reaction style such asradical photopolymerization, cationic photopolymerization, anionicphotopolymerization, or polymerization via photodimerization. It ispreferable that the differences of the refractive index and thepolymerization rate from those of the fluorine-contained photoreactivecompound represented by the formula (1) are as large as possible.

Though the metal fine particles can be incorporated, in a powdery formas they are, into the volume hologram recording photosensitivecomposition, it is preferable, from the viewpoint of the dispersibilitythereof, to disperse the fine particles into any organic solvent andthen incorporate into the composition. The organic solvent can beappropriately selected from examples which will be described later as asolvent used for the preparation of a coating liquid of the hologramrecording photosensitive composition.

A visible laser beam is used to record holograms, and it is preferableto add a sensitizing dye to the volume hologram recording photosensitivecomposition in order to improve the sensitivity at a laser beamwavelength used for hologram-exposure.

It is preferable to use, as the sensitizing dye, a visible lightsensitizing dye (that is, a sensitizing dye which exhibits sensitizingeffect within a visible light range). Examples thereof include cyaninetype, merocyanine type, coumalin type, ketocoumalin type, cyclopentanonetype, cyclohexanone type, thiopyrylium type, quinoline type,styrylquinoline type, thioxanthene type, xanthene type, oxonol type,rhodamine type, and pyrylium salt type dyes.

Specific examples of the cyanine type and merocyanine type dyes include3,3′-dicarboxylethyl-2,2′-thiocyanine bromide,1-carboxymethyl-1′-carboxyethyl-2,2′-quinocyanine bromide,1,3′-diethyl-2,2′-quinothiacyanine iodide, and3-ethyl-5-[(3-ethyl-2(3H)-benzothiazolidene)ethylidene]-2-thioxo-4-oxazolidine.Specific examples of the coumalin type and ketocoumalin type dyesinclude 3-(2′-benzimidazol)7-N,N′-diethylaminocoumalin,3,3′-carbonylbis(7-diethylaminocoumalin), 3,3′-carbonylbiscoumalin,3,3′-carbonylbis(5,7-dimethoxycoumalin), and3,3′-carbonylbis(7-acetoxycoumalin). Specific examples of thecyclopentanone type dye include2,5-bis(4-dimethylaminobenzilidene)cyclopentanone,2,5-bis(4-diethylaminobenzilidene)cylopentanone,2,5-bis(4-dipentylamonobenzilidene)cyclopentanone,2,5-bis[4-(dimethylamino)phenyl]methylene-cyclopentanone,2,5-bis[4-(diethylamino)phenyl]methylene-cyclopentanone,2,5-bis[(2,3,6,7-tetrahydro-1H,5H-benzo[i,j]quinolizine-1-yl)methylene]-cyclopentanone,2,5-bis[2-(1,3-dihydro-1,3,3-trimethyl-2H-indole-2-ylidene)ethylidene]cyclopentanone,2,5-bis[[2-ethylnaphtho[1,2-d]thiazole-2(1H)-ylidene]ethylidene]cyclopentanone,2,5-bis[4′-(dimethylaminocynnamilidene)cyclopentanone,2,5-bis[4′-N-ethyl-N-carbomethoxymethylaminobenzilidene]cyclopentanoneand a sodium salt thereof,2,5-bis(4′-N-methyl-N-cyanoethylaminobenzilidene)cyclopentanone, and2,5-bis(4′-N-ethyl-N-chloroethylaminocynnamilidene)cyclopentanone.Specific examples of the cyclohexanone type dye include2,6-bis{[4-(diethylamino)-phenyl]methylene}-cyclohexanone,2,6-bis{[4-(dimethylamino)-phenyl]methylene}-cyclohexanone,2,6-bis(4′-N-cyanoethylaminobenzilidene)cyclohexanone,2,6-bis(4-dimethylaminobenzilidene)cyclohexanone, and2,6-bis(4-diethylaminobenzilidene)cyclohexanone. However, thesensitizing dye is not limited to these examples.

A sensitizing dye which becomes transparent in a subsequent processafter recording a hologram or which is decomposed or changed instructure by heating or irradiation with ultraviolet rays so as tobecome transparent is preferable in the view of obtaining hightransparency, and it is suitable to a case of requiring hightransparency, for example, optical elements. Preferable examples of thedye which can be made transparent in the subsequent process includecyanine type, merocyanine type, coumalin type, ketocoumalin type, andcyclopentanone type dyes. The transparency referred to herein means thatregions other than hologram recorded portions are transparent with thenaked eye, or that the transmittance is 60% or more at a wavelengthwithin the visible light range (wavelength: 400 to 700 nm).

These sensitizing dyes may be used alone or in the form of a mixture oftwo or more thereof.

When the volume hologram recording photosensitive composition accordingto the present invention contains the binder resin, thefluorine-contained photoreactive compound represented by the formula (1)is used preferably in an amount of 10 to 1000 parts by weight, morepreferably in an amount of 10 to 160 parts by weight per 100 parts byweight of the binder resin. Any conventional fluorine-containedphotoreactive compound, for example, a commercially availablefluorine-contained photoreactive compound (trade name: Viscoat 17F,manufactured by Osaka Organic Chemical Industry Ltd.) can merely becontained up to an amount of about 35 parts by weight per 100 parts byweight of acrylic type binder resin in the view of compatibility withthe other components. In contrast, the fluorine-contained photoreactivecompound represented by the formula (1) can be contained in an amount of1000 parts or more by weight with a result that the Δn can be improved.

The photopolymerization initiator is used preferably in an amount of 0.1to 30 parts by weight, more preferably in an amount of 2 to 20 parts byweight per 100 parts by weight of the binder resin.

The second refractive index modulating component is used preferably inan amount of 10 to 1000 parts by weight, more preferably in an amount of10 to 160 parts by weight per 100 parts by weight of the binder resin.

About the blend ratio between the fluorine-contained photoreactivecompound represented by the formula (1) and the second refractive indexmodulating component, the second refractive index modulating componentis used preferably in an amount of 1 to 1000 parts by weight, morepreferably in 100 to 700 parts by weight per 100 parts by weight of thefluorine-contained photoreactive compound.

The sensitizing dye is used preferably in an amount of 0.01 to 20 partsby weight, more preferably in an amount of 0.01 to 10 parts by weightper 100 parts by weight of the binder resin.

Appropriate amounts of various additives, such as a plasticizer, anadhesiveness control agent (adhesiveness supplier), and an antioxidant,besides the above-mentioned components, may be appropriatelyincorporated into the composition dependently on the purpose of thecomposition.

A coating liquid for the application of the volume hologram recordingphotosensitive composition according to the present invention can beprepared by dissolving the above-mentioned respective materials intoacetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone,benzene, toluene, xylene, chlorobenzene, tetrahydrofuran,methylcellosolve, ethylcellosove, methylcellosove acetate,ethylcellosolve acetate, ethyl acetate, 1,4-dioxane, 1,2-dichloroethane,dichloromethane, chloroform, methanol, ethanol, isopropanol or a mixedsolvent thereof. However, when the fluorine-contained photoreactivecompound or the other blend components are in a liquid form at ambienttemperature, the use amount of the coating solvent can be reduced, andthere may be a case in which no coating solvent is necessary.

The coating liquid is applied to a suitable support such as a substratefilm by spin coating, gravure coating, comma coating, bar coating orsome other coating, and then dried, thereby forming a layer made of thevolume hologram recording photosensitive composition (hereinafterreferred to as a “volume hologram recording material layer”). In thisway, a volume hologram recording photosensitive medium is yielded. Thethickness of the volume hologram recording material layer is preferablyset to 1 to 100 μm, more preferably 2 to 40 μm.

When the fluidity of the volume hologram recording photosensitivecomposition is high, a volume hologram recording section may be formedby putting said volume hologram recording photosensitive compositionair-tightly into a space formed between the support and an opposedcovering material having transparency such as a transparent substrate ora plastic film.

The substrate film of the volume hologram recording photosensitivemedium may be a film having transparency, and examples thereof includepolyethylene, polypropylene, fluorinated polyethylene, fluorinatedpolyvinylidene, polyvinyl chloride, polyvinylidene chloride,ethylene-vinyl alcohol copolymer, polyvinyl alcohol,polymethylmethacrylate, polyethersulfone, polyetheretherketone,polyamide, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer,polyester (such as polyethylene terephthalate), and polyimide films. Thefilm thickness thereof may be from 2 to 200 μm, and is preferably from10 to 50 μm.

When the volume hologram recording material layer after being dried isadhesive, anyone of the films exemplified above as the substrate filmcan be laminated thereon as a protective film. In this case, the contactsurface of the laminated film with the volume hologram recordingmaterial layer may be subjected to releasing treatment in order that thefilm will easily be peeled afterwards.

The volume hologram recording photosensitive medium obtained asdescribed above is a medium wherein a hologram recording section made ofthe volume hologram recording material is disposed on the support. Thehologram recording section is a section containing thefluorine-contained photoreactive compound represented by the formula(1), and is usually the volume hologram recording material layer havinga given thickness but may be in any form in which a hologram can berecorded. Thus, the shape or thickness thereof is not limited.Furthermore, it is unnecessary that the thickness is constant. Asdescribed above, it may be in a form in which the composition in a fluidstate is air-tightly sealed.

The volume hologram recording photosensitive medium according to thepresent invention can be subjected to hologram-exposure by any knownmethod, whereby forming a volume hologram.

For example, a volume hologram is formed in such manner that ifnecessary, the hologram recording material layer of the volume hologramrecording photosensitive medium is beforehand irradiated with relativelyweak light homogenously, thereby polymerizing the photoreactivecomponents, such as the fluorine-contained photoreactive compound, tosome degree, and subsequently a hologram original plate is opposed andadhered to the layer, and the resultant is subjected tohologram-exposure with a visible laser beam from its transparentsubstrate film side.

The recording light which can be used for recording the hologram may beany light that can cause polymerization reaction of thefluorine-contained photoreactive compound represented by the formula(1). Examples thereof include electromagnetic waves having a wavelengthwithin the visible light range and non-visible light range, corpuscularrays such as an electron beam, and radioactive rays or ionizingradioactive rays which is a generic terms including electromagneticwaves and particle beams.

It is preferable to use, as reference light, a laser beam having highcoherency, for example, an argon ion laser (458 nm, 488 nm or 514.5 nm),a krypton ion laser (647.1 nm), a YAG laser (532 nm) or some other laserto form interference fringes and perform exposure.

The volume hologram recording mechanism of the volume hologram recordingphotosensitive composition of the present invention can be considered tobe the same mechanism as has been stated hitherto. That is, when thefilm-form photosensitive composition (that is, the hologram recordingmaterial layer) is subjected to hologram-exposure, thefluorine-contained photoreactive compounds are photopolymerized inregions of the hologram recording material layer in which the light isintensely radiated and a concentration gradient of thefluorine-contained photoreactive compounds is generated accordingly.Thus, the fluorine-contained photoreactive compounds diffuse and movefrom weakly-exposed regions to the intensely exposed regions. As aresult, the fluorine-contained photoreactive compounds become dense orthin in accordance with the intensity or weakness of the interferencelight so as to exhibit a refractive index difference. In this case, therefractive index is lower in regions exposed to light having a largerintensity. This refractive index difference generates interferencefringes to form a volume hologram.

When the film-form hologram recording photosensitive composition whichcomprises the binder resin is subjected to hologram-exposure, theweakly-exposed regions are rich in the binder resin, and becomes closerto the refractive index of the binder resin itself. On the other hand,the intensely exposed regions are rich in the fluorine-containedphotoreactive compound or a polymer produced therefrom, and becomescloser to the refractive index of the fluorine-contained photoreactivecompound itself. Since the refractive index of the fluorine-containedphotoreactive compound is usually lower than that of the binder resin,the refractive index in the weakly-exposed regions, which are rich inthe binder resin, becomes high while the refractive index in theintensely exposed regions, which are rich in the fluorine-containedphotoreactive compound or the polymer produced therefrom, becomes low.As a result thereof, a refractive index modulation can be made verylarge by the refractive index difference between the binder resin andthe fluorine-contained photoreactive compound.

When the volume hologram recording photosensitive composition comprisesthe second refractive index modulating component together with thefluorine-contained photoreactive compound, the fluorine-containedphotoreactive compound and the second refractive index modulatingcomponent diffuse and move so that one having a larger polymerizationrate out of the two is unevenly located in intensely exposed regions andthe other, which has a smaller polymerization rate, is unevenly locatedin weakly-exposed regions. As a result, concentration of thefluorine-contained photoreactive compounds become dense or thin inaccordance with the intensity or weakness of the interference light soas to exhibit a refractive index difference. This refractive indexdifference generates interference fringes to form a volume hologram.

After the hologram-exposure, if one or more selected from swellingtreatment for tuning a hologram reproducing wavelength or tuning thehalf band width of the spectral transmittance curve, entire-surfaceexposure treatment based on uniform light radiation, and heatingtreatment are conducted in an appropriate order as required,polymerization reaction of the photoreactive components in unreactedstate can be promoted, and the refractive index modulation (Δn) can bemade larger, and further the photopolymerization initiator or thesensitizing dye can be inactivated to improve the endurance of thevolume hologram, for example, the heat resistance and moistureresistance, thus being preferable.

In the uniform light radiation after the hologram-exposure, light havinga wavelength within the visible light range may be not necessarily used.Ultraviolet rays may be used. For example, a light source such as asuperhigh-pressure mercury lamp, a high-pressure mercury lamp, a carbonarc, a xenon arc, or a metal halide lamp is used to perform the lightradiation in such a manner that the total exposure quantity will begenerally from about 0.1 to 10000 mJ/cm², preferably from 10 to 4000mJ/cm².

When the heating treatment is conducted after the hologram-exposure,this treatment is conducted instead of the uniform light radiation orbefore or after the uniform light radiation. By the heating treatment,phase-separation is promoted so that the photoreactive components in anunpolymerized status present in the volume hologram recordingphotosensitive composition diffuse and move to complete thepolymerization, thereby increasing and fixing the refractive indexmodulation (Δn). Moreover, the solvent is vaporized so as to make therefractive index modulation (Δn) larger and further so as to improve theendurance of the volume hologram such as the heat resistance or moistureresistance as well as in the case of performing the entire-surfaceexposure to ultraviolet rays. The temperature range for the heatingtreatment is usually from 40 to 150° C., preferably from 40 to 100° C.,and the time for the heating treatment is usually from 5 to 120 minutes,preferably from 5 to 30 minutes.

As described above, hologram-exposure causes interference fringes to begenerated in the hologram recording material layer of the volumehologram recording photosensitive medium according to the presentinvention, so that this layer is converted to a hologram layer, therebyobtaining a volume hologram. According to the present invention, avolume hologram having a large refractive index modulation (Δn) can beproduced and a volume hologram wherein the refractive index modulation(Δn) between its low refractive index regions and its high refractiveindex regions is 0.016 or more, preferably 0.025 or more can beproduced.

The following describes a method of producing a hologram transfer foil,which is one specific example of a product produced using thephotosensitive composition of the present invention. A hologram transferfoil is a product wherein a transfer layer comprising a hologram layeris laid on a support, and this is used to allow a hologram to be easilyapplied to a transfer-receiving surface of various objects.

FIG. 1 illustrates an example of the hologram transfer foil. Thehologram transfer foil 1 has a structure wherein a peelable layer 6, ahologram layer 4 and an adhesive layer 5 are successively laid on onesurface of a support 2. The peelable layer 6, the hologram layer 4 andthe adhesive layer 5 constitute a transfer layer 3.

The method for producing this hologram transfer foil 1 may be a methodof laying the peelable layer 6, a hologram recording material layer, andthe adhesive layer 5 successively on the support 2 by coating and thenrecording a hologram into the hologram recording material layer. Anothermethod may be a method of laying the peelable layer 6 and a hologramrecording material layer successively on the support 2 by coating,recording a hologram into the hologram recording material layer to formthe hologram layer 4, and then laying the adhesive layer 5 on thehologram layer 4 by coating or laminating the adhesive layer 5 formed onanother film on the hologram layer 4.

A preferable method for producing the hologram transfer foil 1 is amethod comprising the processes of providing a film having a hologramrecording material layer and another film having an adhesive layerindividually by a process independent per each film, and afterwardlaying them in combination therewith on a given purpose.

Specifically, the method comprises the processes of providing a firstfilm having a hologram recording material layer, a second film having anadhesive layer, and a third film having a peelable layer individually bya process independent per each film, forming a hologram image within thehologram recording material layer of the first film, and subsequentlylaying the second and third films thereon. The lamination of the firstfilm to the third film can be performed by dry process, which need notuse any solvent, thus being profitable for the producing process.

The method for producing the hologram transfer foil 1 may be a method inwhich a film having a hologram recording material layer and a peelablelayer and a film having an adhesive layer are provided individually by aprocess independent per each film, or a method in which a film having ahologram recording material layer and an adhesive layer and a filmhaving a peelable layer are provided individually by a processindependent per each film.

The above-mentioned first film may be a laminate wherein a hologramrecording material layer is formed on a supporting film such as a PETfilm and further a peelable PET film is laid thereon (PET film/hologramrecording material layer/peelable PET film). The second film may be alaminate wherein an adhesive layer is formed on a peelable PET film andfurther a peelable PET film is formed on this adhesive layer (peelablePET film/adhesive layer/peelable PET film). The adhesive layer may bemade of a thermosensitive adhesive, ordinary adhesive or the like. Thethird film may be a laminate wherein a peelable layer is formed on asupporting film made of PET or the like (PET film/peelable layer).

A specific example of the method of using the above-mentioned first,second and third films to produce a volume hologram type hologramtransfer foil is as follows.

First, the hologram recording material layer of the first film issubjected to hologram-exposure to record a given hologram image therein.Thereafter, the peelable PET film is peeled and removed so that thepeelable layer of the third film is faced and laminated onto thehologram layer of the first film. Next, this is introduced into adeveloping line if necessary, and then subjected to given heatingtreatment and UV treatment to promote a variation in the refractiveindex and fix the image. Furthermore, the supporting film laid on thehologram layer is peeled and removed to make the hologram layer naked.The adhesive layer of the second film is faced and laminated onto thehologram image, thereby yielding a layer structure of the peelable PETfilm/the adhesive layer/the hologram layer/the peelable layer/the PETfilm (supporting film). When the adhesive layer is a thermosensitiveadhesive layer, the adhesive layer can be adhered to the hologram layerby laminating the second film onto the hologram layer under heatingcondition (for example, at 100 to 180° C.). Furthermore, the peelablePET film is peeled therefrom, whereby the hologram transfer foil can beyielded.

FIG. 2 is an explanatory view illustrating an example of transferringoperation using the resultant hologram transfer foil. When the hologramtransfer foil 1 of the present invention is used to perform transfer,the hologram transfer foil 1 of the present invention is laid on asurface of a transfer receiving material 7 to be provided with ahologram in such a manner that the adhesive layer 5 of the transfer foil1 is brought into contact with the transfer receiving material 7, asillustrated in FIG. 2. The upper (i.e., the support 2 side) of thetransfer foil 1 in a portion where a hologram is to be given is thenpressed through a pressing plate 8 or the like. Thereafter, when thetransfer foil is peeled, only the transfer layer in desired portions istransferred onto the surface of the transfer receiving material 7 sothat the hologram can be given. When the adhesive layer 5 is athermosensitive adhesive layer, heating is performed at the same time ofthe pressing through the pressing plate 8 or the like so that thethermosensitive adhesive layer in the desired portions is allowed tomelt and adhere to the transfer receiving material 7. When the adhesivelayer 5 is an ordinary adhesive layer, the hologram layer is allowed toadhere to the transfer receiving material 7 by only the pressing throughthe pressing plate 8 or the like.

As described above, in the volume hologram recording photosensitivecomposition according to the present invention, a fluorine-containedphotoreactive compound having a structure represented by the formula (1)is used as a refractive index modulating component. Thisfluorine-contained photoreactive compound has a very low refractiveindex and is further superior in compatibility with other blendcomponents such as a binder resin and polymerization reactivity anddiffusing/moving ability at the time of hologram-exposure. Therefore,this compound is suitable for a low refractive index type refractiveindex modulating component. By incorporating this component, as arefractive index modulating component, into a volume hologram recordingphotosensitive composition, superior sensitivity and refractive indexmodulating effect can be obtained.

By adding, to this fluorine-contained photoreactive compound, otherblend components such as a photopolymerization initiator, a binderresin, metal fine particles and a sensitizing dye appropriately, anon-fluid volume hologram recording layer can be formed on a substrate.Thus, a dry-developable volume hologram recording photosensitive mediumhaving a good sensitivity and a large refractive index modulation can beobtained.

Accordingly, provided are a volume hologram recording material, a volumehologram recording medium and a volume hologram which are superior inhologram recording performances, such as a refractive index modulationand sensitivity.

When a binder resin capable of forming a covalent bond with thefluorine-contained photoreactive compound is used as the binder resin inthe present invention, the layer strength and the heat resistance of thehologram layer can be improved.

In this case, it is possible to provide a volume hologram recordingmaterial, a volume hologram recording medium and a volume hologram whichare superior in not only hologram recording performances, such as arefractive index modulation, sensitivity and transparency but alsophysical properties such as strength and heat resistance. Thus, it isexpected that these are applied to wide fields such as an opticalelement or the like.

When the binder resin capable of forming a covalent bond with thefluorine-contained photoreactive compound is a binder resin thefunctional group of which can be photopolymerized with a photoreactivegroup of the fluorine-contained photoreactive compound at the time ofhologram-exposure, the fluorine-contained photoreactive compound is alsopolymerized with the binder resin in intensely exposed regions so thatthe reactivity thereof is increased. Consequently, the refractive indexmodulation and the sensitivity can be further improved.

EXAMPLES

The present invention will be described hereafter by way of theexamples.

1. Production of a Volume Hologram

Example 1

(1) Preparation of a Volume Hologram Recording PhotosensitiveComposition

The following components were mixed to yield a volume hologram recordingphotosensitive composition.

<Composition>

Acrylic resin (trade name: BR-73, manufactured by Mitsubishi Rayon Co.,Ltd.): 100 parts by weight

Fluorine-contained photoreactive compound represented by the followingformula (5) (synthesized with reference to methods described in JP-B No.54-11284, 59-22712, and 6-60116, J. Fluorine Chem., 73, 151 (1995) andso on): 70 parts by weight

Irgacure 784 (manufactured by Ciba Specialty Chemicals, inc.): 5 partsby weight

Methanol: 30 parts by weight

Methyl ethyl ketone: 30 parts by weight

(2) Production of a Volume Hologram Recording Photosensitive Medium

The above-mentioned volume hologram recording photosensitive compositionwas applied onto a polyethylene terephthalate (referred to as PEThereinafter) film (trade name: LUMIRROR T-60, manufactured by TorayIndustries, Inc.) having a thickness of 38 μm with a bar coater to forma hologram recording material layer having a thickness of 20 μm afterbeing dried. In this way, a volume hologram recording photosensitivemedium was produced.

(3) Production of a Volume Hologram

The volume hologram recording photosensitive medium was laminated onto amirror in such a manner that its hologram recording material layercontacted the mirror. An argon laser beam having a wavelength of 514.5nm was radiated into the medium from its PET film side so as to conducthologram-exposure. In this way, a volume hologram was recorded.

Next, the interference fringes were fixed by heating and irradiationwith ultraviolet rays, to yield a volume hologram.

Example 2

A volume hologram was produced in the same conditions as in Example 1except that the composition of the volume hologram recordingphotosensitive composition was changed as follows.

<Composition>

Vinyl acetate-acrylic copolymer resin (copolymer of vinyl acetate/ethylacrylate/acrylic acid (composition ratio=50/45/5)) prepared by radicalpolymerization in a usually way, weight average molecularweight=100000): 100 parts by weight

Fluorine-contained photoreactive compound represented by the followingformula (5) (synthesized with reference to methods described in JP-B No.54-11284, 59-22712, and 6-60116, J. Fluorine Chem., 73, 151 (1995) andso on): 70 parts by weight

Fluorene skeleton-contained compound represented by the followingformula (6) (synthesized by a known method from bisphenoxyethanolfluorene and epichlorohydrin): 80 parts by weight

Diaryl iodonium salt (trade name: PI2074, manufactured by Rhodia): 5parts by weight

3-Ethyl-5-[(3-ethyl-2(3H)-benzothiazolilidene)ethylidene]-2-thioxo-4-oxazolidinone(trade name: NK-1473, manufactured by Hayashibara BiochemicalLaboratories, Inc.): 2 parts by weight

Methanol: 30 parts by weight

Methyl ethyl ketone: 30 parts by weight

Example 3

A volume hologram was produced in the same conditions as in Example 1except that the composition of the volume hologram recordingphotosensitive composition was changed as follows.

<Composition>

Vinyl acetate-acrylic copolymer resin (copolymer of vinyl acetate/ethylacrylate/acrylic acid (composition ratio=50/45/5)) prepared by radicalpolymerization in a usually way, weight average molecularweight=100000): 100 parts by weight

Fluorine-contained photoreactive compound represented by the followingformula (5) (synthesized with reference to methods described in JP-B No.54-11284, 59-22712, and 6-60116, J. Fluorine Chem., 73, 151 (1995) andso on): 70 parts by weight,

Polyethylene glycol diacrylate (trade name: A-400, manufactured byShin-Nakamura Chemical Co., Ltd.): 20 parts by weight

Fluorene skeleton-contained compound represented by the followingformula (6) (synthesized by a known method from bisphenoxyethanolfluorene and epichlorohydrin): 80 parts by weight

Diaryl iodonium salt (trade name: PI2074, manufactured by Rhodia): 5parts by weight

3-Ethyl-5-[(3-ethyl-2(3H)-benzothiazolilidene)ethylidene]-2-thioxo-4-oxazolidinone(trade name: NK-1473, manufactured by Hayashibara BiochemicalLaboratories, Inc.): 2 parts by weight

Methanol: 30 parts by weight

Methyl ethyl ketone: 30 parts by weight

Example 4

A volume hologram was produced in the same conditions as in Example 1except that the composition of the volume hologram recordingphotosensitive composition was changed as follows.

<Composition>

Fluorine-contained photoreactive compound represented by the followingformula (5) (synthesized with reference to methods described in JP-B No.54-11284, 59-22712, and 6-60116, J. Fluorine Chem., 73, 151 (1995) andso on): 70 parts by weight

Polyethylene glycol diacrylate (trade name: A-400, manufactured byShin-Nakamura Chemical Co., Ltd.): 20 parts by weight

Fluorene skeleton-contained compound represented by the followingformula (6) (synthesized by a known method from bisphenoxyethanol andepichlorohydrin): 80 parts by weight

Diaryl iodonium salt (trade name: PI2074, manufactured by Rhodia): 5parts by weight

3-Ethyl-5-[(3-ethyl-2(3H)-benzothiazolilidene)ethylidene]-2-thioxo-4-oxazolidinone(trade name: NK-1473, manufactured by Hayashibara BiochemicalLaboratories, Inc.): 2 parts by weight,

Methanol: 30 parts by weight

Methyl ethyl ketone: 30 parts by weight

Example 5

A volume hologram was produced in the same conditions as in Example 1except that the composition of the volume hologram recordingphotosensitive composition was changed as follows.

<Composition>

Fluorine-contained photoreactive compound represented by the followingformula (5) (synthesized with reference to methods described in JP-B No.54-11284, 59-22712, and 6-60116, J. Fluorine Chem., 73, 151 (1995) andso on): 70 parts by weight

Polyethylene glycol diacrylate (trade name: A-400, manufactured byShin-Nakamura Chemical Co., Ltd.): 20 parts by weight

Bisphenol type epoxy oligomer (trade name: Epikote 1007, manufactured byJapan Epoxy Resins Co., Ltd.): 180 parts by weight

Diaryl iodonium salt (trade name: PI2074, manufactured by Rhodia): 10parts by weight

3-Ethyl-5-[(3-ethyl-2(3H)-benzothiazolilidene)ethylidene]-2-thioxo-4-oxazolidinone(trade name: NK-1473, manufactured by Hayashibara BiochemicalLaboratories, Inc.): 2 parts by weight

Methanol: 50 parts by weight

Methyl ethyl ketone: 50 parts by weight

Example 6

A volume hologram was produced in the same conditions as in Example 1except that the composition of the volume hologram recordingphotosensitive composition was changed as follows.

<Composition>

Vinyl acetate-acrylic copolymer resin (copolymer of vinyl acetate/ethylacrylate/acrylic acid (composition ratio=50/45/5)) prepared by radicalpolymerization in a usually way, weight average molecularweight=100000): 100 parts by weight

Fluorine-contained photoreactive compound represented by the followingformula (7) (trade name: E-7432, manufactured by Daikin Industries,Ltd.): 70 parts by weight

Diaryl iodonium salt (trade name: PI2074, manufactured by Rhodia): 5parts by weight

3-Ethyl-5-[(3-ethyl-2(3H)-benzothiazolilidene)ethylidene]-2-thioxo-4-oxazolidinone(trade name: NK-1473, manufactured by Hayashibara BiochemicalLaboratories, Inc.): 2 parts by weight

Methanol: 30 parts by weight

Methyl ethyl ketone: 30 parts by weight

Example 7

A volume hologram was produced in the same conditions as in Example 1except that the composition of the volume hologram recordingphotosensitive composition was changed as follows.

<Composition>

Acrylic resin (trade name: BR-73, manufactured by Mitsubishi Rayon Co.,Ltd.): 100 parts by weight

Fluorine-contained photoreactive compound represented by the followingformula (7) (trade name: E-7432, manufactured by Daikin Industries,Ltd.): 70 parts by weight,

Polyethylene glycol diglycidyl ether (trade name: DENACOL EX-821,manufactured by Nagase ChemteX Corporation): 30 parts by weight

Diaryl iodonium salt (trade name: PI2074, manufactured by Rhodia): 5parts by weight

3-Ethyl-5-[(3-ethyl-2(3H)-benzothiazolilidene)ethylidene]-2-thioxo-4-oxazolidinone(trade name: NK-1473, manufactured by Hayashibara BiochemicalLaboratories, Inc.): 2 parts by weight

Methanol: 30 parts by weight

Methyl ethyl ketone: 30 parts by weight

Example 8

A volume hologram was produced in the same conditions as in Example 1except that the composition of the volume hologram recordingphotosensitive composition was changed as follows.

<Composition>

Acrylic resin (trade name: BR-73, manufactured by Mitsubishi Rayon Co.,Ltd.): 100 parts by weight

Fluorine-contained photoreactive compound represented by the followingformula (7) (trade name: E-7432, manufactured by Daikin Industries,Ltd.): 150 parts by weight

9,9-Bis(4-acryloxydiethoxyphenyl)fluorene (synthesized by a known methodfrom bisphenoxyethanol fluorene and acrylic acid): 150 parts by weight

Diaryl iodonium salt (trade name: PI2074, manufactured by Rhodia): 10parts by weight

3-Ethyl-5-[(3-ethyl-2(3H)-benzothiazolilidene)ethylidene]-2-thioxo-4-oxazolidinone(trade name: NK-1473, manufactured by Hayashibara BiochemicalLaboratories, Inc.): 2 parts by weight

Methanol: 50 parts by weight

Methyl ethyl ketone: 50 parts by weight

Example 9

A volume hologram was produced in the same conditions as in Example 1except that the composition of the volume hologram recordingphotosensitive composition was changed as follows.

<Composition>

Acrylic resin (trade name: BR-73, manufactured by Mitsubishi Rayon Co.,Ltd.): 100 parts by weight

Fluorine-contained photoreactive compound represented by the followingformula (7) (trade name: E-7432, manufactured by Daikin Industries,Ltd.): 150 parts by weight

4,4′-bis(β-methacryloyloxyethylthio)diphenylsulfone: 150 parts by weight

Diaryl iodonium salt (trade name: PI2074, manufactured by Rhodia): 10parts by weight

3-Ethyl-5-[(3-ethyl-2(3H)-benzothiazolilidene)ethylidene]-2-thioxo-4-oxazolidinone(trade name: NK-1473, manufactured by Hayashibara BiochemicalLaboratories, Inc.): 2 parts by weight

Methanol: 50 parts by weight

Methyl ethyl ketone: 50 parts by weight

Example 10

A volume hologram was produced in the same conditions as in Example 1except that the composition of the volume hologram recordingphotosensitive composition was changed as follows.

<Composition>

Acrylic resin (trade name: BR-73, manufactured by Mitsubishi Rayon Co.,Ltd.): 100 parts by weight

Fluorine-contained photoreactive compound represented by the followingformula (7) (trade name: E-7432, manufactured by Daikin Industries,Ltd.): 75 parts by weight

Polyethyleneglycol diglycidyl ether (trade name: DENACOL EX-821,manufactured by Nagase ChemteX Corporation): 50 parts by weight

9,9-Bis(4-acryloxydiethoxyphenyl)fluorene (synthesized by a known methodfrom bisphenoxyethanol fluorene and acrylic acid): 80 parts by weight

Diaryl iodonium salt (trade name: PI2074, manufactured by Rhodia): 5parts by weight

3-Ethyl-5-[(3-ethyl-2(3H)-benzothiazolilidene)ethylidene]-2-thioxo-4-oxazolidinone(trade name: NK-1473, manufactured by Hayashibara BiochemicalLaboratories, Inc.): 2 parts by weight

Methanol: 30 parts by weight

Methyl ethyl ketone: 30 parts by weight

Example 11

A volume hologram was produced in the same conditions as in Example 1except that the composition of the volume hologram recordingphotosensitive composition was changed as follows.

<Composition>

Epoxy group-contained acrylic resin (trade name: Blemer CP-50S,manufactured by NOF Corporation): 100 parts by weight

Fluorine-contained photoreactive compound represented by the followingformula (5) (synthesized with reference to methods described in JP-B No.54-11284, 59-22712, and 6-60116, J. Fluorine Chem., 73, 151 (1995) andso on): 70 parts by weight

9,9-Bis(4-acryloxydiethoxyphenyl)fluorene (synthesized by a known methodfrom bisphenoxyethanol fluorene and acrylic acid): 80 parts by weight

Diaryl iodonium salt (trade name: PI2074, manufactured by Rhodia): 5parts by weight

3-Ethyl-5-[(3-ethyl-2(3H)-benzothiazolilidene)ethylidene]-2-thioxo-4-oxazolidinone(trade name: NK-1473, manufactured by Hayashibara BiochemicalLaboratories, Inc.): 2 parts by weight

Methanol: 30 parts by weight

Methyl ethyl ketone: 30 parts by weight

Example 12

A volume hologram was produced in the same conditions as in Example 1except that the composition of the volume hologram recordingphotosensitive composition was changed as follows.

<Composition>

Vinyl acetate-acrylic copolymer resin (copolymer of vinyl acetate/ethylacrylate/acrylic acid (composition ratio=50/45/5)) prepared by radicalpolymerization in a usually way, weight average molecularweight=100000): 100 parts by weight

Fluorine-contained photoreactive compound represented by the followingformula (5) (synthesized with reference to methods described in JP-B No.54-11284, 59-22712, and 6-60116, J. Fluorine Chem., 73, 151 (1995) andso on): 70 parts by weight

Titania-dispersed solution (titania particle size=30 nm, MIBK solution,solid content=30%): 30 parts by weight

Diaryl iodonium salt (trade name: PI2074, manufactured by Rhodia): 5parts by weight

3-Ethyl-5-[(3-ethyl-2(3H)-benzothiazolilidene)ethylidene]-2-thioxo-4-oxazolidinone(trade name: NK-1473, manufactured by Hayashibara BiochemicalLaboratories, Inc.): 2 parts by weight

Methanol: 30 parts by weight

Methyl ethyl ketone: 30 parts by weight

Example 13

(1) Preparation of Zirconia Fine Particles onto Which an EthylenicallyUnsaturated Bond was Introduced

There was used a coupling agent, 3-acryloxypropyltrimethoxysilane havingan ethylenically unsaturated double bond (trade name: KBM 5103,manufactured by Shin-Etsu Chemical Co., Ltd.). The coupling agent wasadded to a zirconia dispersed solution (zirconia particle size: 30 nm,MIBK solution) prepared so as to have a solid content of 30% in such amanner that the concentration of the coupling agent would be 2% byweight of the zirconia while the solution was stirred. The solution wasfurther stirred, and then subjected to filtration and drying so as toyield target zirconia fine particles onto which the ethylenicallyunsaturated bond was introduced. As the method for surface-treatingmetal fine particles, dry, wet, blend and other methods are known.According to anyone of the methods, surfaces of the metal fine particlescan be coupling-treated.

(2) Production of a Volume Hologram Recording PhotosensitiveComposition, a Volume Hologram Recording Photosensitive Medium, and aVolume Hologram

A volume hologram was produced in the same conditions as in Example 1except that the composition of the volume hologram recordingphotosensitive composition was changed as follows.

<Composition>

Acrylic resin (trade name: BR-73, manufactured by Mitsubishi Rayon Co.,Ltd.): 20 parts by weight

Fluorine-contained photoreactive compound represented by the followingformula (7) (trade name: E-7432, manufactured by Daikin Industries,Ltd.): 75 parts by weight

The above-mentioned zirconia fine particles onto which the ethylenicallyunsaturated bond was introduced: 60 parts by weight

Diaryl iodonium salt (trade name: PI2074, manufactured by Rhodia): 3parts by weight

3-Ethyl-5-[(3-ethyl-2(3H)-benzothiazolilidene)ethylidene]-2-thioxo-4-oxazolidinone(trade name: NK-1473, manufactured by Hayashibara BiochemicalLaboratories, Inc.): 1 part by weight

Methanol: 30 parts by weight

Methyl ethyl ketone: 30 parts by weight

Example 14

(1) Preparation of an Organic-Inorganic Hybrid Polymer Starting Solution

Ethyl acrylate (manufactured by KANTO KAGAKU) and3-acryloxypropyltrimethoxysilane (trade name: KBM 5103, manufactured byShin-Etsu Chemical Co., Ltd.) with 6:4 in terms of mole ratio arepolymerized for 8 hours under reflux using benzene as a solvent andbenzoyl peroxide as a polymerization initiator. After the end of thereaction, unreacted products and benzene were removed to purify andsubjected to drying under decompression to yield a polymer.

The resultant polymer was dissolved into acetone, and thereto were addedwater, hydrochloric acid, and zirconium butoxide (trade name: ORGATIXZA60, manufactured by Matsumoto Chemical Industry Co., Ltd.) so as toadvance sol-gel reaction, thereby yielding a target organic-inorganichybrid polymer starting solution.

(2) Production of a Volume Hologram Recording PhotosensitiveComposition, a Volume Hologram Recording Photosensitive Medium, and aVolume Hologram

A volume hologram was produced in the same conditions as in Example 1except that the composition of the volume hologram recordingphotosensitive composition was changed as follows.

<Composition>

The above-mentioned organic-inorganic hybrid polymer solution: 100 partsby weight (solid content)

Fluorine-contained photoreactive compound represented by the followingformula (7) (trade name: E-7432, manufactured by Daikin Industries,Ltd.): 75 parts by weight

Diaryl iodonium salt (trade name: PI2074, manufactured by Rhodia): 5parts by weight,

3-Ethyl-5-[(3-ethyl-2(3H)-benzothiazolilidene)ethylidene]-2-thioxo-4-oxazolidinone(trade name: NK-1473, manufactured by Hayashibara BiochemicalLaboratories, Inc.): 2 parts by weight

Methanol: 30 parts by weight

Methyl ethyl ketone: 30 parts by weight

Example 15

A volume hologram was produced in the same conditions as in Example 1except that the composition of the volume hologram recordingphotosensitive composition was changed as follows.

<Composition>

Acrylic resin (trade name: BR-73, manufactured by Mitsubishi Rayon Co.,Ltd.): 100 parts by weight

Fluorine-contained photoreactive compound represented by the followingformula (8) (synthesized with reference to methods described in JP-B No.54-11284, 59-22712 and 6-60116, JP-A No. 2000-336082, J. Fluorine Chem.,73, 151 (1995) and so on): 75 parts by weight

1,6-Hexanediol diglycidyl ether (trade name: DENACOL EX-212,manufactured by Nagase ChemteX Corporation): 50 parts by weight

9,9-Bis(4-acryloxydiethoxyphenyl)fluorene (synthesized by a known methodfrom bisphenoxyethanol fluorene and acrylic acid): 80 parts by weight

Diaryl iodonium salt (trade name: PI2074, manufactured by Rhodia): 5parts by weight

3-Ethyl-5-[(3-ethyl-2(3H)-benzothiazolilidene)ethylidene]-2-thioxo-4-oxazolidinone(trade name: NK-1473, manufactured by Hayashibara BiochemicalLaboratories, Inc.): 2 parts by weight

Methanol: 30 parts by weight

Methyl ethyl ketone: 30 parts by weight

Example 16

A volume hologram was produced in the same conditions as in Example 1except that the composition of the volume hologram recordingphotosensitive composition was changed as follows.

<Composition>

Vinyl acetate-acrylic copolymer resin (copolymer of vinyl acetate/ethylacrylate/acrylic acid (composition ratio=50/45/5)) prepared by radicalpolymerization in a usually way, weight average molecularweight=100000): 100 parts by weight

Fluorine-contained photoreactive compound represented by the followingformula (8) (synthesized with reference to methods described in JP-B No.54-11284, 59-22712 and 6-60116, JP-A No. 2000-336082, J. Fluorine Chem.,73, 151 (1995) and so on): 70 parts by weight

Trimethylolpropane triacrylate (trade name: A-TMPT, manufactured byShin-Nakamura Chemical Co., Ltd.): 20 parts by weight

1,6-Hexanediol diglycidyl ether (trade name: DENACOL EX-212,manufactured by Nagase ChemteX Corporation): 30 parts by weight

4,4′-Bis(β-methacryloyloxyethylthio)diphenylsulfone: 80 parts by weight

Diaryl iodonium salt (trade name: PI2074, manufactured by Rhodia): 5parts by weight

3-Ethyl-5-[(3-ethyl-2(3H)-benzothiazolilidene)ethylidene]-2-thioxo-4-oxazolidinone(trade name: NK-1473, manufactured by Hayashibara BiochemicalLaboratories, Inc.): 2 parts by weight

Methanol: 30 parts by weight

Methyl ethyl ketone: 30 parts by weight

Example 17

A volume hologram was produced in the same conditions as in Example 1except that the composition of the volume hologram recordingphotosensitive composition was changed as follows.

<Composition>

Polyvinyl acetate (weight average molecular weight converted topolystyrene molecular weight=100000): 100 parts by weight

Fluorine-contained photoreactive compound represented by the followingformula (9) (synthesized with reference to methods described in JP-B No.54-11284, 59-22712 and 6-60116, J. Fluorine Chem., 73, 151 (1995) and soon): 25 parts by weight

1,6-Hexanediol diglycidyl ether (trade name: DENACOL EX-212,manufactured by Nagase ChemteX Corporation): 70 parts by weight

9,9-Bis(4-acryloxydiethoxyphenyl)fluorene (trade name: BPEFA,manufactured by Osaka Gas Co., Ltd.): 80 parts by weight

Diaryl iodonium salt (trade name: PI2074, manufactured by Rhodia): 5parts by weight

3-Ethyl-5-[(3-ethyl-2(3H)-benzothiazolilidene)ethylidene]-2-thioxo-4-oxazolidinone(trade name: NK-1473, manufactured by Hayashibara BiochemicalLaboratories, Inc.): 2 parts by weight

1-Butanol: 30 parts by weight

Methyl ethyl ketone: 30 parts by weight

Example 18

A volume hologram was produced in the same conditions as in Example 1except that the composition of the volume hologram recordingphotosensitive composition was changed as follows.

<Composition>

Polyvinyl acetate (weight average molecular weight converted topolystyrene molecular weight=100000): 100 parts by weight

Fluorine-contained photoreactive compound represented by the followingformula (9) (synthesized with reference to methods described in JP-B No.54-11284, 59-22712 and 6-60116, J. Fluorine Chem., 73, 151 (1995) and soon): 25 parts by weight

1,6-Hexanediol diglycidyl ether (trade name: DENACOL EX-212,manufactured by Nagase ChemteX Corporation): 70 parts by weight

9,9-Bis(4-acryloxydiethoxyphenyl)fluorene (trade name: BPEFA,manufactured by Osaka Gas Co., Ltd.): 80 parts by weight

Diaryl iodonium salt (trade name: PI2074, manufactured by Rhodia): 5parts by weight

3,9-Diethyl-3′-carboxymethyl-2,2′-thiacarbocyanine iodonium salt: 1 partby weight

1-Butanol: 30 parts by weight

Methyl ethyl ketone: 30 parts by weight

Example 19

A volume hologram was produced in the same conditions as in Example 1except that the composition of the volume hologram recordingphotosensitive composition was changed as follows and the wavelength forthe hologram-exposure was changed from 514.5 nm to 488 nm.

<Composition>

Polyvinyl acetate (weight average molecular weight converted topolystyrene molecular weight=100000): 100 parts by weight

Fluorine-contained photoreactive compound represented by the followingformula (9) (synthesized with reference to methods described in JP-B No.54-11284, 59-22712 and 6-60116, J. Fluorine Chem., 73, 151 (1995) and soon): 25 parts by weight

1,6-Hexanediol diglycidyl ether (trade name: DENACOL EX-212,manufactured by Nagase ChemteX Corporation): 70 parts by weight

9,9-Bis(4-acryloxydiethoxyphenyl)fluorene (trade name: BPEFA,manufactured by Osaka Gas Co., Ltd.): 80 parts by weight

Diaryl iodonium salt (trade name: PI2074, manufactured by Rhodia): 5parts by weight

2,6-Bis(4-dimethylaminobenzilidene)cyclohexanone (manufactured by MidoriKagaku Co., Ltd.): 1 part by weight

1-Butanol: 30 parts by weight

Methyl ethyl ketone: 30 parts by weight

Example 20

A volume hologram was produced in the same conditions as in Example 1except that the composition of the volume hologram recordingphotosensitive composition was changed as follows.

<Composition>

Polyvinyl acetate (weight average molecular weight converted topolystyrene molecular weight=100000): 100 parts by weight

Fluorine-contained photoreactive compound represented by the followingformula (9) (synthesized with reference to methods described in JP-B No.54-11284, 59-22712 and 6-60116, J. Fluorine Chem., 73, 151 (1995) and soon): 25 parts by weight

1,6-Hexanediol diglycidyl ether (trade name: DENACOL EX-212,manufactured by Nagase ChemteX Corporation): 70 parts by weight

9,9-Bis(4-acryloxydiethoxyphenyl)fluorene (trade name: BPEFA,manufactured by Osaka Gas Co., Ltd.): 80 parts by weight

2-Mercaptobenzothiazole (available from Ardrich): 5 parts by weight

2,5-Dinitrobenzyl tosylate: 5 parts by weight

2,5-Bis(4-dipentylaminobenzilidene)cyclopentanone: 1 part by weight

1-Butanol: 30 parts by weight

Methyl ethyl ketone: 30 parts by weight

Comparative Example 1

A volume hologram was produced in the same conditions as in Example 1except that the fluorine-contained photoreactive compound in the volumehologram recording photosensitive composition of Example 1 was changedto polyethylene glycol diacrylate (trade name: A-400, manufactured byShin-Nakamura Chemical Co., Ltd.).

Comparative Example 2

A volume hologram was produced in the same conditions as in Example 1except that the fluorine-contained photoreactive compound in the volumehologram recording photosensitive composition of Example 1 was changedto polyethylene glycol diglycidyl ether (trade name: DENACOL EX-821,manufactured by Nagase ChemteX Corporation) and Irgacure 784 was changedto diaryl iodonium salt (trade name: PI2074, manufactured by Rhodia).

Comparative Example 3

A volume hologram was produced under the same conditions as in Example 1except that the fluorine-contained photoreactive compound in the volumehologram recording photosensitive composition of Example 1 was changedto 1H, 1H, 2H, 2H-heptadecafluorodecyl acrylate (trade name: Viscoat17F, manufactured by Osaka Organic Chemistry Industry Ltd.). As aresult, the hologram recording material layer whitely clouded. Thus, novolume hologram was unable to be recorded.

Comparative Example 4

A volume hologram was produced under the same conditions as in Example 1except that the fluorine-contained photoreactive compound in the volumehologram recording photosensitive composition of Example 1 was changedto a polyfunctional fluorine-contained photoreactive compound (tradename: ART-3, manufactured by KYOEISYA CHEMICAL Co., Ltd.). As a result,the hologram recording material layer whitely clouded. Thus, no volumehologram was unable to be recorded.

2. Evaluation of the Refractive Index Modulation (Δn):

A spectrophotometer (trade name: UVPC-3100, manufactured by ShimadzuCorporation) was used to measure the transmittance, and the diffractionefficiency η=(B−A)/B was calculated by determining the peaktransmittance being as “A” and the base transmittance being as “B” inthe resultant spectral transmittance curve (see FIG. 3).

From the value of the diffraction efficiency, the refractive indexmodulation (Δn) was calculated from the following theoretical equationbased on Kogelnik's coupled-wave theory (Bell Syst. Tech. J., 48, 2909(1969)):η=tan h ²(π(Δn)d/λ cos θ₀)wherein d represents the thickness of the photosensitive material layer,λ represents the wavelength of the recording laser, and θ₀ representsthe incident angle of the recording laser into the photosensitivematerial.

The evaluation results of the refractive index modulations are shown inTable 1. In each of Examples, the hologram had a large refractive indexmodulation and was bright. In particular, in Example 17 using thefluorine-contained photoreactive compound represented by the formula(9), an especially large refractive-index modulation was obtained.

TABLE 1 Refractive index modulation (Δn) Example 1 0.023 Example 2 0.031Example 3 0.028 Example 4 0.016 Example 5 0.025 Example 6 0.023 Example7 0.024 Example 8 0.036 Example 9 0.032 Example 10 0.036 Example 110.021 Example 12 0.026 Example 13 0.028 Example 14 0.031 Example 150.033 Example 16 0.031 Example 17 0.07 Example 18 0.035 Example 19 0.03Example 20 0.04 Comparative 0.007 Example 1 Comparative 0.008 Example 2Comparative Cloudiness Example 3 Comparative Cloudiness Example 4

We claim:
 1. A hologram transfer foil in which a peelable layer, ahologram layer and an adhesive layer are successively laid on onesurface of a support, wherein the hologram layer is formed using aphotosensitive composition comprising a binder resin containing anorganic-inorganic hybrid polymer and a fluorine-containing photoreactivecompound represented by the following formula (1):R¹—R³—(CF₂)n-R⁴—R²  Formula (1) wherein each of R¹ and R² isindependently an epoxy group or an oxetanyl group, and each of R³ and R⁴is independently a single bond or a bivalent hydrocarbon group having 1to 5 carbon atoms, and n is an integer of 1 or more.
 2. The hologramtransfer foil according to claim 1, wherein each of R¹ and R² is anepoxy group.
 3. The hologram transfer foil according to claim 1, whereineach of R¹ and R² in the formula (1) is an oxetanyl group represented bythe following formula (2):

wherein R⁵ is a hydrogen atom or an alkyl group having 1 to 10 carbonatoms.
 4. The hologram transfer foil according to claim 1, wherein eachof R³ and R⁴ in the formula (1) is independently a single bond or alinear hydrocarbon group.
 5. The hologram transfer foil according toclaim 1, wherein the photosensitive composition further comprises aphotopolymerization initiator.
 6. The hologram transfer foil accordingto claim 1, wherein the photosensitive composition further comprises asecond refractive index modulating component other than thefluorine-containing photoreactive compound.
 7. The hologram transferfoil according to claim 1, wherein a combination of the photosensitivecomposition is any one selected from the group consisting of thefollowing (1) to (3): (1) a combination comprising thefluorine-containing photosensitive compound represented by the formula(1), a binder resin having a refractive index different from that of thefluorine-containing photosensitive compound, and a radicalphotopolymerizable compound which is the second refractive indexmodulating component having a refractive index different from that ofthe fluorine-containing photosensitive compound; (2) a combinationcomprising the fluorine-containing photosensitive compound representedby the formula (1), a binder resin having a refractive index differentfrom that of the fluorine-containing photosensitive compound, and acationic photopolymerizable compound which is the second refractiveindex modulating component having a refractive index different from thatof the fluorine-containing photosensitive compound; (3) a combinationcomprising the fluorine-containing photosensitive compound representedby the formula (1), a binder resin having a refractive index differentfrom that of the fluorine-containing photosensitive compound, a radicalphotopolymerizable compound which is the second refractive indexmodulating component having a refractive index different from that ofthe fluorine-containing photosensitive compound, and a cationicphotopolymerizable compound which is the second refractive indexmodulating component having a refractive index different from that ofthe fluorine-containing photosensitive compound.
 8. The hologramtransfer foil according to claim 1, wherein the photosensitivecomposition further comprises metal fine particles having a refractiveindex different from that of the fluorine-containing photosensitivecompound represented by the formula (1).
 9. The hologram transfer foilaccording to claim 1, wherein the photosensitive composition furthercomprises a sensitizing dye which gets transparent by light-exposure ortreatment after the light-exposure.
 10. The hologram transfer foilaccording to claim 9, wherein the sensitizing dye is at least oneselected from the group consisting of cyanine type dyes, merocyaninetype dyes, coumarin type dyes, ketocoumarin type dyes, andcyclopentanone type dyes.
 11. The hologram transfer foil according toclaim 1, wherein the photosensitive composition further comprises afluorene skeleton-containing photopolymerizable compound having arefractive index different from that of the fluorine-containingphotosensitive compound represented by the formula (1).
 12. A method forproducing a hologram transfer foil, in which a peelable layer, ahologram layer and an adhesive layer are successively laid on onesurface of a support, wherein the hologram layer is formed by forming ahologram recording material layer using a photosensitive compositioncomprising a binder resin containing an organic-inorganic hybrid polymerand a fluorine-containing photoreactive compound represented by thefollowing formula (1):R¹—R³—(CF₂)n-R⁴—R²  Formula (1) wherein each of R¹ and R² isindependently an epoxy group or an oxetanyl group, and each of R³ and R⁴is independently a single bond or a bivalent hydrocarbon group having 1to 5 carbon atoms, and n is an integer of 1 or more, and by subjectingthe hologram recording material layer to hologram-exposure.
 13. Ahologram transfer foil in which a peelable layer, a hologram layer andan adhesive layer are successively laid on one surface of a support,wherein the hologram layer is formed using a photosensitive compositioncomprising a binder resin containing an organic-inorganic hybrid polymerand a fluorine-containing photoreactive compound represented by thefollowing formula (1):R¹—R³—(CF₂)n-R⁴—R²  Formula (1) wherein each of R¹ and R² isindependently an acryloyl group or a methacryloyl group, and each of R³and R⁴ is independently a single bond or a bivalent hydrocarbon grouphaving 1 to 5 carbon atoms, and n is an integer of 1 or more.
 14. Amethod for producing a hologram transfer foil, in which a peelablelayer, a hologram layer and an adhesive layer are successively laid onone surface of a support, wherein the hologram layer is formed byforming a hologram recording material layer using a photosensitivecomposition comprising a binder resin containing an organic-inorganichybrid polymer and a fluorine-containing photoreactive compoundrepresented by the following formula (1):R¹—R³—(CF₂)n-R⁴—R²  Formula (1) wherein each of R¹ and R² isindependently an acryloyl group or a methacryloyl group, and each of R³and R⁴ is independently a single bond or a bivalent hydrocarbon grouphaving 1 to 5 carbon atoms, and n is an integer of 1 or more, and bysubjecting the hologram recording material layer to hologram-exposure.